The influence of several additives upon the properties of the system AOT/isoctane/water has been investigated. The presence of crown ethers (18-crown-6) and kryptand complexes (kryptand 222, kryptand 221 and kryptand 211) have an important effect upon the electrical percolation phenomena. Low macrocyclic concentrations hinder the electrical percolation phenomenon. This effect seems to be due to the ability of macrocycles to, complex ions and transfer them to the interface. Medium and high macrocyclic concentrations favor the electrical percolation, and this effect is related to their interfacial association to the AOT head groups. The observed behavior has been explained in terms of critical packing parameter, and it is compared with the influence of small additives as electrolytes or small organic molecules.